EP2125767B1 - Pyran derivatives, process of preparation and use thereof in perfumery and flavouring - Google Patents

Pyran derivatives, process of preparation and use thereof in perfumery and flavouring Download PDF

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Publication number
EP2125767B1
EP2125767B1 EP07847567.0A EP07847567A EP2125767B1 EP 2125767 B1 EP2125767 B1 EP 2125767B1 EP 07847567 A EP07847567 A EP 07847567A EP 2125767 B1 EP2125767 B1 EP 2125767B1
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Prior art keywords
group
present
hydrogen atom
methyl
absent
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German (de)
French (fr)
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EP2125767A2 (en
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Caroline Plessis
Jean Mane
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V Mane Fils SAS
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V Mane Fils SAS
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Priority claimed from EP06291857A external-priority patent/EP1927593A1/en
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Priority to PL07847567T priority Critical patent/PL2125767T3/en
Priority to EP07847567.0A priority patent/EP2125767B1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/205—Heterocyclic compounds
    • A23L27/2052—Heterocyclic compounds having oxygen or sulfur as the only hetero atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/002—Aftershave preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations

Definitions

  • the present invention relates to the field of fragrances and flavours. More particularly, the invention relates to pyran derivatives, the process of preparation thereof, and their use in the field of perfumery and flavouring.
  • fragment and “fragrant”, as used herein, are used interchangeably whenever a compound or a mixture of compounds is referred to, which is intended to pleasantly stimulate the sense of smell.
  • flavouring relates to the flavouring of any liquid or solid, human or animal, in particular of drinks, dairy products, ice creams, soups, sauces, dips, dishes, meat products, culinary assistances, salted biscuits or snacks. It also means the flavouring of beers, wines and tobaccos.
  • organoleptic compound such as for example fragrances and flavours, as used herein, refers to compounds of the invention which stimulate the sense of smell or taste, and are thus perceived as having a characteristic odour and/or flavour.
  • masking is meant reducing or eliminating malodour or bad flavour perception generated by one or more molecules entering in the composition of a product.
  • isomer in the present invention, means molecules having the same chemical formula, which means same number and types of atoms, but in which the atoms are arranged differently.
  • isomers geometric isomers, optical isomers and stereoisomers.
  • alkyl or "alkyl group”, in the present invention, means any linear or branched saturated hydrocarbon chain, having preferably 1, 2, 3, 4 or 5 carbon atoms and herein referred to as C 1-5 alkyl group, such as for example methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl.
  • alkenyl or "alkenyl group”, in the present invention, means any linear or branched mono or poly unsaturated hydrocarbon chain, having preferably 2, 3, 4 or 5 carbon atoms and herein referred to as C 2-5 alkenyl group, such as for example ethenyl, propenyl, butenyl, or pentenyl.
  • cycloalkyl or "cycloalkyl group”, in the present invention, means any cyclic saturated hydrocarbon chain having preferably 5, 6 or 7 carbon atoms, such as for example cyclopentyl, cyclohexyl and cycloheptyl, substituted or not by an alkyl or alkenyl group as described above.
  • cycloalkenyl or "cycloalkenyl group”, in the present invention, means any cyclic mono or poly unsaturated hydrocarbon chain having preferably 5, 6 or 7 carbon atoms, such as for example cyclopentenyl, cyclohexenyl and cycloheptenyl, substituted or not by an alkyl or alkenyl as described above.
  • cycloalkylacetaldehyde in the present invention, represents an acetaldehyde substituted by a cycloalkyl group.
  • cycloalkenylacetaldehyde in the present invention, represents an acetaldehyde substituted by a cycloalkenyl group.
  • Tetrahydropyran and dihydropyran derivatives belong to an important class of fragrant ingredients and a large work has already been done to prepare known compounds, such as for example Rose Oxide and similar derivatives, from linear or branched alkyl and alkenyl aldehydes, as described in US 3,681,263 and in WO 04/009749 , or from benzylic aldehydes as described in CH 655 932 .
  • esters or ethers of pyranols have been found of interest in the aromatic industry as shown in US 4,963,285 , US 4,962,090 .
  • JP25-7911 discloses ethers, including 2-(1-cyclohexylethyl)-tetrahydro-2H-pyran, useful as perfume.
  • EP0189144 discloses a pyran derivative mixture wherein the 2,4-dimethyl-3-cyclohexenyl moiety is directly attached position 2 of the pyran ring, and the use thereof in perfume compositions.
  • EP0746552 discloses tetrahydropyran derivatives wherein the cyclopentyl or cyclopentenyl moiety is directly attached to position 5 of the pyran ring, and the use thereof as odorants
  • US4963285 discloses pyran-4-ol derivatives having a C2-C4 straight chain or branched chain alkyl or alkenyl group in position 2 of the pyran ring and the use thereof for enhancing the aroma of consumable materials.
  • US 2,452,977 relates to a process for the production of cyclic compounds; according to this process, an unsaturated alcohol is reacted with an aldehyde to produce a cyclic compound having an oxygen atom within the ring. Some resulting compounds are pyrans.
  • the Applicant focused on lateral cyclic chains, more specifically on cycloalkylacetaldehydes and cycloalkenylacetaldehydes as starting materials.
  • This invention thus relates to pyran derivatives of general formula (I) wherein
  • the invention relates to pyran derivatives of general formula (I) as described above, wherein
  • preferred pyran derivatives of general formula (I) as described above are those wherein
  • preferred pyran derivatives of general formula (I) as described above are selected in the group comprising 4-methylene-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran, 4-methylene-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(
  • pyran derivatives of the invention are of general formula (I) wherein
  • the invention relates to a process for the preparation of the pyran derivatives of the invention, said process being characterized in that a compound of general formula (A) wherein
  • the process further comprises a step to convert the aldehyde (A) into an acetal of general formula (C) wherein
  • (A) and/or (B) and/or (C) is used as an optically pure isomer.
  • the invention relates to the process as described above, wherein compound (A) or compound (C) is reacted, in presence of an acid, with compound (B), and from the resulting mixture, the different compounds of formula (I), wherein X is OZ, Z being a hydrogen atom or a linear or branched C 1-5 alkyl or C 2-5 alkenyl group, or wherein X is absent, are separated.
  • compound (A) is reacted with compound (B), in presence of an acid, and from the resulting mixture, the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I) wherein X is absent, and then subjected to an esterification reaction, in order to obtain compounds of formula (I) wherein X is OC(O)R10.
  • the esterification reaction may be performed by usual procedures known by one skilled in the art.
  • compound (A) is reacted with compound (B), in presence of an acid, and from the resulting mixture, the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I), wherein X is absent and then subjected to an alkylation reaction in order to obtain compounds of formula (I) wherein X is OZ, Z being a linear or branched C 1-5 alkyl or C 2-5 alkenyl group.
  • the alkylation reaction may be performed by usual procedures known by one skilled in the art.
  • the invention relates to the process as described above, wherein compound (A) is reacted with compound (B) and the resulting mixture of pyran derivatives is subjected to a dehydration reaction in presence of an acid, said process resulting in the manufacturing of compounds of formula (I) wherein X is absent, and a double bond at the 4 position is present.
  • Separation steps may be performed by any techniques known from one skilled in the art.
  • compositions comprising at least one compound of formula (II), and/or at least one compound of general formula (III) and/or at least one compound of general formula (IV), and optionally (V) and/or (VI) wherein
  • This invention relates to the compounds of formula (I), as described above, but also to any of their various isomers.
  • the invention relates to the use of the compounds of formula (I) as described above.
  • the invention relates to the use of at least one compound or of the composition as described above, in the perfumery field for the preparation of perfumed bases and concentrates, fragrances, perfumes and similar products; topic compositions; cosmetic compositions such as for example face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades; cleaning products, such as for example softeners, detergents, air deodorizers and household cleaning supplies. Therefore, the invention also relates to a fragrant composition including at least one compound of formula (I) or one or more isomers of a compound of formula (I).
  • the invention relates to the use of at least one compound or of the composition as described above, as flavouring agents for the preparation of flavouring compositions or articles, such as for example drinks, dairy products, ice creams, soups, sauces, dips, dishes, meat products, culinary assistances, salted biscuits or snacks and also beers, wines and tobaccos. Therefore, the invention also relates to a flavoured composition including at least one compound of formula (I) or one or more isomers of a compound of formula (I).
  • the invention relates to the use of the compounds or composition as described above, as masking agents of odours and/or flavours, and to any pharmaceutical, cosmetic or food composition containing at least one compound of formula (I) or one or more isomers of a compound of formula (I). Therefore, this invention also relates to any composition comprising at least one compound of formula (I), as herein described, in combination with any suitable excipient, especially pharmaceutical or cosmetic or dietary excipient.
  • the compounds of the invention may be used alone or in combination with other perfuming or flavouring ingredients, solvents, additives or fixatives, commonly used and that the man skilled in the art is able to choose in regard of the desired effect and the nature of the product to perfume or flavour.
  • This invention includes, for example, any composition comprising one or more isomers of a compound of formula (I).
  • this invention relates to a composition comprising at least two or three isomers of a compound of formula (I).
  • the compounds of the invention are used in a concentration comprised in a range from 0.001% to 99% in weight, in particular from 0.1% to 50% in weight, more particularly from 0.1% to 30% in weight. It is known by the man skilled in the art that these values depend on the nature of the composition/article to be perfumed and/or flavoured, the desired intensity of the perfume and/or flavour, and the nature of the other ingredients present in said composition or article.
  • the compounds of the invention are used in an olfactory effective amount.
  • olfactory effective amount is meant a level or amount of fragrant/flavouring compound in a material at which the incorporated compound exhibits a sensory effect.
  • the distilled product (82°C/ 0.8 torr) consists in a mixture of isomers (A), (B) and (C) in a 27:16:57 ratio.
  • Its odour is powerful, hesperidic (bitter orange, petitgrain), green (galbanum, peas).
  • the different isomers are obtained separately by a fine fractionation distillation with a packed column under partial reflux.
  • Each isomer is a mixture of 2 diastereoisomers.
  • a mixture of isomers, prepared in example 1, is treated under a normal pressure of hydrogen in ethanol with catalytic amount of palladium on charcoal (5%) to give the desired tetrahydropyran.
  • the crude product obtained after filtration of the reaction mixture on Clarcel® is purified by distillation (88°C/ 0.7 torr). It consists in four couples of diastereoisomers (2 major and 2 minor, the ratio between them is 36:42:10:12). Its odour is bitter orange, woody, a bit dusty/musky.
  • a mixture of isomers (A), (B) and (C) in a 63:14:23 ratio was prepared, according to example 1, starting from hydrogenated campholenaldehyde.
  • Example 5 Fragrance composition containing the (A)/(B)/(C) mixture obtained in example 1
  • a base perfuming composition was prepared as described from the following ingredients: ABRAC NERYL ACETATE 5 BENZYL ACETATE 5 BERGAMYL ACETATE 70 GERANYL ACETATE 7 LINALYL ACETATE 45 TERPENYL ACETATE 60 ACETYL ISOEUGENOL 5 PHENYLETHYLALCOHOL 130 BENZALDEHYDE 2 ALDEHYDE C10 2 CYCLAMEN ALDEHYDE ® 25 ANISALDEHYDE 20 VELVIONE ® 5 GLOBANONE ® 5 METHYL BENZOATE 2 CETONE MIEL 5 ETHYL LINALOL 100 FLOROL ® 45 BOIS DE GAIAC ESS.

Description

  • The present invention relates to the field of fragrances and flavours. More particularly, the invention relates to pyran derivatives, the process of preparation thereof, and their use in the field of perfumery and flavouring.
  • The terms "fragrance" and "fragrant", as used herein, are used interchangeably whenever a compound or a mixture of compounds is referred to, which is intended to pleasantly stimulate the sense of smell.
  • The terms "flavour", and "flavouring", as used herein, are used interchangeably whenever a compound or a mixture of compounds is referred to, which is intended to stimulate the sense of taste and smell. Also in the meaning of the invention, the term flavouring relates to the flavouring of any liquid or solid, human or animal, in particular of drinks, dairy products, ice creams, soups, sauces, dips, dishes, meat products, culinary assistances, salted biscuits or snacks. It also means the flavouring of beers, wines and tobaccos.
  • The term "organoleptic compound", such as for example fragrances and flavours, as used herein, refers to compounds of the invention which stimulate the sense of smell or taste, and are thus perceived as having a characteristic odour and/or flavour.
  • By the term "masking" is meant reducing or eliminating malodour or bad flavour perception generated by one or more molecules entering in the composition of a product.
  • The term "isomer", in the present invention, means molecules having the same chemical formula, which means same number and types of atoms, but in which the atoms are arranged differently. The term "isomer" includes structural isomers, geometric isomers, optical isomers and stereoisomers.
  • The term "alkyl" or "alkyl group", in the present invention, means any linear or branched saturated hydrocarbon chain, having preferably 1, 2, 3, 4 or 5 carbon atoms and herein referred to as C1-5 alkyl group, such as for example methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl.
  • The term "alkenyl" or "alkenyl group", in the present invention, means any linear or branched mono or poly unsaturated hydrocarbon chain, having preferably 2, 3, 4 or 5 carbon atoms and herein referred to as C2-5 alkenyl group, such as for example ethenyl, propenyl, butenyl, or pentenyl.
  • The term "cycloalkyl" or "cycloalkyl group", in the present invention, means any cyclic saturated hydrocarbon chain having preferably 5, 6 or 7 carbon atoms, such as for example cyclopentyl, cyclohexyl and cycloheptyl, substituted or not by an alkyl or alkenyl group as described above.
  • The term "cycloalkenyl" or "cycloalkenyl group", in the present invention, means any cyclic mono or poly unsaturated hydrocarbon chain having preferably 5, 6 or 7 carbon atoms, such as for example cyclopentenyl, cyclohexenyl and cycloheptenyl, substituted or not by an alkyl or alkenyl as described above.
  • The term "cycloalkylacetaldehyde", in the present invention, represents an acetaldehyde substituted by a cycloalkyl group.
  • The term "cycloalkenylacetaldehyde", in the present invention, represents an acetaldehyde substituted by a cycloalkenyl group.
  • Tetrahydropyran and dihydropyran derivatives belong to an important class of fragrant ingredients and a large work has already been done to prepare known compounds, such as for example Rose Oxide and similar derivatives, from linear or branched alkyl and alkenyl aldehydes, as described in US 3,681,263 and in WO 04/009749 , or from benzylic aldehydes as described in CH 655 932 .
  • Similarly, esters or ethers of pyranols have been found of interest in the aromatic industry as shown in US 4,963,285 , US 4,962,090 .
  • JP25-7911 discloses ethers, including 2-(1-cyclohexylethyl)-tetrahydro-2H-pyran, useful as perfume.
  • EP0189144 discloses a pyran derivative mixture wherein the 2,4-dimethyl-3-cyclohexenyl moiety is directly attached position 2 of the pyran ring, and the use thereof in perfume compositions.
  • EP0746552 discloses tetrahydropyran derivatives wherein the cyclopentyl or cyclopentenyl moiety is directly attached to position 5 of the pyran ring, and the use thereof as odorants
  • US4963285 discloses pyran-4-ol derivatives having a C2-C4 straight chain or branched chain alkyl or alkenyl group in position 2 of the pyran ring and the use thereof for enhancing the aroma of consumable materials.
  • US 2,452,977 relates to a process for the production of cyclic compounds; according to this process, an unsaturated alcohol is reacted with an aldehyde to produce a cyclic compound having an oxygen atom within the ring. Some resulting compounds are pyrans.
  • The need of new compounds is of great importance for the development of the flavour and fragrance industry, which recently had to face stricter international regulatory requirements about the use of certain materials, as well as environmental concerns and customer demands for improved performance. Being able of manufacturing new fragrant compounds is therefore a challenge.
  • When exploring further the pyran derivatives in order to identify new fragrant compounds, the Applicant focused on lateral cyclic chains, more specifically on cycloalkylacetaldehydes and cycloalkenylacetaldehydes as starting materials.
  • None of the above-cited document mentions nor suggests a possible use of cycloalkylacetaldehyde , or cycloalkenylacetaldehyde to prepare pyran derivatives, and of course, as the resulting pyran derivatives are new, there is no prior art information regarding their possible olfactive or organoleptic properties.
  • This invention thus relates to pyran derivatives of general formula (I)
    Figure imgb0001
     wherein
    • Y =
      Figure imgb0002
       wherein R'1, R'2 and R'3 are each independently a hydrogen atom or a methyl group or an ethyl group, at least one of R'1, R'2 and R'3 being a methyl or an ethyl group,
      wherein the dotted lines represent a double bond and is present or not.
      • R1, R2, R3, R4 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group, and
      • X is present or absent,
      • when X is present,
        • o R5, R6, R7, R8, R9 are all present, and X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group
      • when X is absent, a double bond involving the carbon atom at the 4 position is present and
        • o R7, R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
        • o R5, R6, and R7 are present, and one of R8 or R9 is present and the other one is absent, or
        • o R7 is a =C(R11) (R12) group and R5, R6, R8, R9 are present,
      • and when they are present, each of R5-R12 group is, independently, a hydrogen atom, or a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  • In a specific embodiment, the invention relates to pyran derivatives of general formula (I) as described above, wherein
    • Y is one of a (Y1), (Y2), (Y3) or (Y4) group
      Figure imgb0003
      Figure imgb0004
    • R1, R2, R3, R4 are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group, and
    • X is present or absent,
    • when X is present,
      • o R5, R6, R7, R8, R9 are all present, and X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group
    • when X is absent, a double bond involving the carbon atom at the 4 position is present and
      • o R7, R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
      • o R5, R6, and R7 are present, and one of R8 or R9 is present and the other one is absent, or
      • o R7 is a = C(R11) (R12) group and R5, R6, R8, R9 are present,
    • and when they are present, each of R5-R12 group is, independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  • In another embodiment, preferred pyran derivatives of general formula (I) as described above, are those wherein
    • Y is a 5-, 6- or 7-membered ring, preferably a 5-membered ring, optionally methyl or ethyl mono- or polysubstituted, and optionally unsaturated, or Y is a (Y1), (Y2), (Y3), (Y4) group,
    • one of R3 or R4 is an hydrogen atom, and the other one is a methyl group
    • R7 is a =CH2 group and X is absent; or
    • R7 is a methyl group and X is present or absent ; when R7 is a methyl group and X is present, X is an hydrogen atom or an OZ group, wherein Z is an hydrogen atom or a R10 group or a C(O)R10 group; when R7 is a methyl group and X is absent, a double bond involving the carbon atom at the 4 position is present and
      • o R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
      • o R5, R6, are present, and one of R8 or R9 is present and the other one is absent,
    • R1,R2 and R10 are each independently a hydrogen atom, or a linear or branched C1-5 alkyl or C2-5 alkenyl group
    • When present, R5, R6, R8, R9 are each a hydrogen atom.
  • In still another embodiment, preferred pyran derivatives of general formula (I) as described above, are selected in the group comprising 4-methylene-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran, 4-methylene-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-4-(3-methyl-but-3-enyloxy)-2-(2,2,3-trimethyl-cyclo-pentylmethyl)-tetrahydropyran.
  • According to another embodiment, pyran derivatives of the invention are of general formula (I) wherein
    • Y is a 5-, 6-, or 7-membered ring, optionally methyl or ethyl mono or polysubstituted, and saturated; or
    • Y is a 5- or 7-membered ring, optionally methyl or ethyl mono or polysubstituted, and polyunsaturated; or
    • Y is a 5- or 6-membered ring, optionally methyl or ethyl mono or polysubstituted, mono or di-unsaturated, provided that the double bond is not in position 1', or
    • Y is a 7-membered ring, optionally methyl or ethyl mono or polysubstituted, mono-unsaturated, or
    • R1, R2, R3, R4 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group, and
    • X is present or absent,
    • when X is present,
      • o R5, R6, R7, R8, R9 are all present, and X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group
    • when X is absent, a double bond involving the carbon atom at the 4 position is present and
      • o R7, R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
      • o R5, R6, and R7 are present, and one of R8 or R9 is present and the other one is absent, or
      • o R7 is a =C(R11)(R12) group and R5, R6, R8, R9 are present,
    • and when they are present, each of R5-R12 group is, independently, a hydrogen atom, or a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  • In a second aspect, the invention relates to a process for the preparation of the pyran derivatives of the invention, said process being characterized in that a compound of general formula (A)
    Figure imgb0005
     wherein
    • Y is a 5-, 6- or 7-membered ring, preferably a 5-membered ring, optionally methyl or ethyl mono- or polysubstituted, and optionally unsaturated,
    • R1 and R2 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    is reacted, in presence of an acid, with a compound of general formula (B)
    Figure imgb0006
     wherein
    R3, R4, R5, R6, R7, R8 and R9 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl group, or a linear or branched C2-5 alkenyl group.
  • According to an embodiment of the invention, the process further comprises a step to convert the aldehyde (A) into an acetal of general formula (C)
    Figure imgb0007
     wherein
    • Y is a 5-, 6- or 7-membered ring, preferably a 5-membered ring, optionally methyl or ethyl mono- or polysubstituted, and optionally unsaturated,
    • R1, R2, are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    • Z is a R10 group wherein R10 is a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    prior to the reaction with the alcohol (B).
  • According to an embodiment, (A) and/or (B) and/or (C) is used as an optically pure isomer.
  • In another embodiment, the invention relates to the process as described above, wherein compound (A) or compound (C) is reacted, in presence of an acid, with compound (B), and from the resulting mixture, the different compounds of formula (I), wherein X is OZ, Z being a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group, or wherein X is absent, are separated.
  • According to another embodiment of the invention, compound (A) is reacted with compound (B), in presence of an acid, and from the resulting mixture, the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I) wherein X is absent, and then subjected to an esterification reaction, in order to obtain compounds of formula (I) wherein X is OC(O)R10.
    The esterification reaction may be performed by usual procedures known by one skilled in the art.
  • According to another embodiment of the invention, compound (A) is reacted with compound (B), in presence of an acid, and from the resulting mixture, the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I), wherein X is absent and then subjected to an alkylation reaction in order to obtain compounds of formula (I) wherein X is OZ, Z being a linear or branched C1-5 alkyl or C2-5 alkenyl group.
    The alkylation reaction may be performed by usual procedures known by one skilled in the art.
  • In another particular embodiment, the invention relates to the process as described above, wherein compound (A) is reacted with compound (B) and the resulting mixture of pyran derivatives is subjected to a dehydration reaction in presence of an acid, said process resulting in the manufacturing of compounds of formula (I) wherein X is absent, and a double bond at the 4 position is present.
  • Separation steps may be performed by any techniques known from one skilled in the art.
  • Another aspect of the invention is a composition comprising at least one compound of formula (II), and/or at least one compound of general formula (III) and/or at least one compound of general formula (IV), and optionally (V) and/or (VI)
    Figure imgb0008
    Figure imgb0009
     wherein
    • Y is a 5-, 6- or 7-membered ring, preferably a 5-membered ring, optionally methyl or ethyl mono- or polysubstituted, and optionally unsaturated,
    • R1, R2, R3, R4, R5, R6, R7, R8, R9 are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    • Z is a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group or a group C(O)R10 wherein R10 is a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  • This invention relates to the compounds of formula (I), as described above, but also to any of their various isomers.
  • In a last aspect, the invention relates to the use of the compounds of formula (I) as described above.
  • In a first embodiment, the invention relates to the use of at least one compound or of the composition as described above, in the perfumery field for the preparation of perfumed bases and concentrates, fragrances, perfumes and similar products; topic compositions; cosmetic compositions such as for example face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades; cleaning products, such as for example softeners, detergents, air deodorizers and household cleaning supplies. Therefore, the invention also relates to a fragrant composition including at least one compound of formula (I) or one or more isomers of a compound of formula (I).
  • In a second embodiment, the invention relates to the use of at least one compound or of the composition as described above, as flavouring agents for the preparation of flavouring compositions or articles, such as for example drinks, dairy products, ice creams, soups, sauces, dips, dishes, meat products, culinary assistances, salted biscuits or snacks and also beers, wines and tobaccos. Therefore, the invention also relates to a flavoured composition including at least one compound of formula (I) or one or more isomers of a compound of formula (I).
  • In a third embodiment, the invention relates to the use of the compounds or composition as described above, as masking agents of odours and/or flavours, and to any pharmaceutical, cosmetic or food composition containing at least one compound of formula (I) or one or more isomers of a compound of formula (I). Therefore, this invention also relates to any composition comprising at least one compound of formula (I), as herein described, in combination with any suitable excipient, especially pharmaceutical or cosmetic or dietary excipient.
  • The compounds of the invention may be used alone or in combination with other perfuming or flavouring ingredients, solvents, additives or fixatives, commonly used and that the man skilled in the art is able to choose in regard of the desired effect and the nature of the product to perfume or flavour. This invention includes, for example, any composition comprising one or more isomers of a compound of formula (I). According to a preferred embodiment, this invention relates to a composition comprising at least two or three isomers of a compound of formula (I).
  • In another embodiment, in the uses as described above, the compounds of the invention are used in a concentration comprised in a range from 0.001% to 99% in weight, in particular from 0.1% to 50% in weight, more particularly from 0.1% to 30% in weight. It is known by the man skilled in the art that these values depend on the nature of the composition/article to be perfumed and/or flavoured, the desired intensity of the perfume and/or flavour, and the nature of the other ingredients present in said composition or article. According to a preferred embodiment, the compounds of the invention are used in an olfactory effective amount. By olfactory effective amount is meant a level or amount of fragrant/flavouring compound in a material at which the incorporated compound exhibits a sensory effect.
  • Following examples detail the preparation processes of the compounds of the invention and their use. These examples are presented with an only goal of illustration.
    • Example 1: Preparation of 4-Methylene-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-tetrahydro-pyran (A) 4-Methyl-6-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran (B) 4-Methyl-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran (C)
  • A mixture of 1 equivalent of campholenaldehyde and 2 equivalents of 3-methyl-3-buten-1-ol in toluene, with catalytic amount of PTSA, is heated under reflux to remove the formed water. After completion of the reaction (3 hours), the mixture is cooled down and diluted with toluene. After washing with a saturated bicarbonate solution and brine, the organic phase is dried over MgSO4, filtered and the solvents are evaporated to afford a crude oil.
  • The distilled product (82°C/ 0.8 torr) consists in a mixture of isomers (A), (B) and (C) in a 27:16:57 ratio.
    Figure imgb0010
  • Its odour is powerful, hesperidic (bitter orange, petitgrain), green (galbanum, peas).
  • The different isomers are obtained separately by a fine fractionation distillation with a packed column under partial reflux.
    Each isomer is a mixture of 2 diastereoisomers.
  • 1H-NMR (CDCl3, 200MHz) : common protons δ (ppm) 0,75 (s, 3H), 0,97 (s, 3H), 1.25-2.5 (m, 7H), 1.59 (s, 3H), 5,22 (m, 1H).
    • Characteristic protons:
    1. (A) δ (ppm) 1,25-2,5 (m, 2H), 3.2-3.7 (m, 3H), 4.7 (m, 2H).
    2. (B) δ (ppm) 1.68 (s, 3H), 3.9-4.2 (m, 3H), 5,32 (m, 1H).
    3. (C) δ (ppm) 1.68 (s, 3H), 3.2-3.7 (m, 1H), 3.9-4.2 (m, 2H), 5.4 (m, 1H).
  • IR (film, cm-1): 796m, 1014m, 1095m, 1122s, 1138m, 1360m, 1382m, 1437m, 1445m, 1463m, 2864s, 2930s, 2955s.
    MS [e/m (%)]: 220(M+, 12), 149(5), 135(4), 119(8), 108(100), 93(59), 79(19), 67(35), 53(20), 41(48).
    • Example 2: Preparation of 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydro-pyran
  • A mixture of isomers, prepared in example 1, is treated under a normal pressure of hydrogen in ethanol with catalytic amount of palladium on charcoal (5%) to give the desired tetrahydropyran. The crude product obtained after filtration of the reaction mixture on Clarcel® is purified by distillation (88°C/ 0.7 torr). It consists in four couples of diastereoisomers (2 major and 2 minor, the ratio between them is 36:42:10:12).
    Its odour is bitter orange, woody, a bit dusty/musky. 1H-NMR (CDCl3, 200MHz): common protons δ (ppm) 0.46 & 0.48 (s, 3H), 0.65-0.87 (m, 6H), 0.90-1.30 (m, 4H), 1.30-2.20 (m, 9H), 3.10-3.75 (m, 2H).
    Major isomers: Characteristic protons δ (ppm) 0.90 (d, J=6.1Hz) & 0.91 (d, J=6.2Hz) : 3H ; 3.85-4.0 (m, 1H).
    Minor isomers: Characteristic protons δ (ppm) 1.01 (d, 1H, J=7.1Hz) & 1.02 (d, 1H, J=7.1Hz) : 3H ; 3.10-3.75 (m, 1H). 13C-NMR (CDCl3, 60MHz):
    Major isomers: 13.9 & 14.26, 22.36 & 24.40, 25.37 & 25.46, 28.11 & 28.39, 30.14 & 30.26; 30.27 & 30.41, 34.75 & 34.82, 37.40 & 37.51, 40.21 & 41.87, 42.03 & 42.35, 44.90 & 44.96, 46.11 & 47.01, 67.99 & 68.12, 76.37 & 77.18.
    Minor isomers (selected data): 13.90 & 14.26, 18.72 & 19.18, 24.78 & 24.94, 28.0 & 28.32, 32.4 & 32.62, 35.44 & 35.96, 37.19 & 38.82, 44.87, 47.4.
    IR (film, cm-1): 1095s, 1177m, 1366m, 1374m, 1386m, 1456m, 1466m, 2838m, 2869s, 2926s, 2952s.
    MS [e/m (%)]: 224 (M+, 1), 99(100), 55(18), 43(19), 41(17).
    • Example 3: Preparation of 4-Methylene-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydro-pyran (A) 4-Methyl-6-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran (B) 4-Methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran (C)
  • Figure imgb0011
  • A mixture of isomers (A), (B) and (C) in a 63:14:23 ratio was prepared, according to example 1, starting from hydrogenated campholenaldehyde.
  • Its odour is similar to that of example 1.
    • Main isomers (A):
  • 1H-NMR (CDCl3, 200MHz): δ (ppm) 0.45-0.55 (m, 3H), 0.75-0.85 (m, 6H), 1.0-1.3 (m, 2H), 1.3-1.55 (m, 3H), 1.55-2.0 (m, 5H), 2.0-2.4 (m, 2H), 3.1-3.4 (m, 2H), 3.9-4.05 (m, 1H), 4.65-4.75 (m, 2H).
    13C-NMR (CDCl3, 60MHz) : δ (ppm) 13.89 & 14.23, 25.34 & 25.46, 28.04 & 28.43, 30.11 & 30.24, 35.22 & 35.27, 37.20, 40.81 & 42.24, 44.87 & 44.95, 46.05 & 47.07, 46.14 & 46.19, 68.55 & 68.64, 77.63 & 78.54, 108.01 & 108.17, 144.75 & 1.44.97.
    (B) Isomers (Characteristic protons): δ (ppm) 3.9-4.05 (m, 3H), 5.25-5.30 (m, 1H).
    13C-NMR (CDCl3, 60MHz, selected data): δ (ppm) 63.12 & 63.44, 72.53 & 72.72, 123.67 & 125.10.
    (C) Isomers (Characteristic protons): δ (ppm) 3.4-3.65 (m, 1H), 3.95-4.15 (m, 2H).
    13C-NMR (CDCl3, 60MHz, selected data): δ (ppm) 65.76 & 65.84, 73.39 & 73.72, 119.65 & 119.74.
    • Example 4: 4-methyl-4-(3-methyl-but-3-enyloxy)-2-(2,2,3-trimethyl-cyclo-pentylmethyl)-tetrahydropyran
  • 4-Methyl-4-(3-methyl-but-3-enyloxy)-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetra-hydropyran was obtained under the conditions used in example 3 and was separated from the other derivatives by fine fractionation.
  • It consists in a trans/cis (60:40) mixture of isomers.
    Figure imgb0012
  • Its odour is not powerful, bitter orange.
    Major diastereoisomers, trans isomers:
    1H-NMR (CDCl3, 200MHz): δ (ppm) 0.49 (s, 3H), 0.82 (d, 3H, J = 10.1Hz), 0.83 (s, 3H), 1.0-1.9 (m, 12H), 1.28 (s, 3H), 1.74 (s, 3H), 2.24 (t, 2H, J = 7.1Hz), 3.2-3.5 (m, 2H), 3.50 (t, 2H, J = 7.2Hz), 4.74 (m, 2H).
    13C-NMR (CDCl3 60MHz): δ (ppm) 13.91 & 14.29, 21.12 & 21.34, 23.0, 25.38 & 25.46, 28.08 & 28.25, 30.11. & 30.23, 37.24 & 37.35, 37.4 & 37.49, 38.65, 42.08 & 42.39, 43.11 & 44.41, 44.88 & 44.98, 46.11 & 47.0, 58.95, 65.05 & 65.13, 72.60 & 72.66, 73.79 & 74.74, 111.15, 143.24.
    MS [e/m (%)]: 308(M+, 1), 293(2), 223(23), 109(10), 99(72), 97(10), 69(100), 55(10), 43(11), 41(36).
    IR (film, cm-1): 642w, 887m, 1078m, 1104s, 1144m, 1177m, 1251w, 1271w, 1374m, 1453m, 1466m, 1650w, 2869s, 2951s.
    • Minor diastereoisomers, cis isomers:
  • 1H-NMR (CDCl3, 200MHz), selected data: δ (ppm) 0.48 (s, 3H), 1.27 (s, 3H), 3.49 (t, 2H, J = 7.2Hz).
    13C-NMR (CDCl3, 60MHz), selected data: δ (ppm) 111.36, 143.39.
    MS [e/m (%)]: 308(M+, 1), 293(9), 223(11), 222(11), 221(37), 112(25), 109(12), 99(26), 97(28), 95(12), 69(100), 55(16), 43(17), 41(50).
    IR (film, cm-1): 642w, 887m, 1078m, 1104s, 1144m, 1177m, 1251w, 1271w, 1374m, 1453m, 1466m, 1650w, 2869s, 2951s.
    • Example 5: Fragrance composition containing the (A)/(B)/(C) mixture obtained in example 1
  • A base perfuming composition was prepared as described from the following ingredients:
    ABRAC NERYL ACETATE 5
    BENZYL ACETATE 5
    BERGAMYL ACETATE 70
    GERANYL ACETATE 7
    LINALYL ACETATE 45
    TERPENYL ACETATE 60
    ACETYL ISOEUGENOL 5
    PHENYLETHYLALCOHOL 130
    BENZALDEHYDE 2
    ALDEHYDE C10 2
    CYCLAMEN ALDEHYDE® 25
    ANISALDEHYDE 20
    VELVIONE® 5
    GLOBANONE® 5
    METHYL BENZOATE 2
    CETONE MIEL 5
    ETHYL LINALOL 100
    FLOROL® 45
    BOIS DE GAIAC ESS. 2
    METHYL DIHYDROJASMONATE 40
    IONONE ALPHA 30
    IONONE BETA 10
    MAYOL® 30
    METHYL ISOEUGENOL 2
    NEROLINE® 15
    LINALOL OXIDE 3
    TERPINEOL 85
    TETRAHYDROLINALOL 30
    VANILLINE 1
    ACETOPHENONE 10% DPG 5
    PHENYLACETIC ACID 10% DPG 2
    CITRONELLAL C 10% DPG. 2
    INDOLAROME® 10% DPG 5
    800
  • To this base composition of the honeysuckle type were added 10 parts in weight of the (A)/(B)/(C) mixture of isomers obtained in example 1. The novel composition thus obtained showed a greener note, reminding petit-grain essence, with a light orange blossom undertone. Furthermore, the (A)/(B)/(C) mixture imparts freshness to the composition, those interesting aspects of the new fragrance composition have been appreciated in alcoholic, as well as in a shower gel and in a cream base.

Claims (14)

  1. Pyran derivatives of general formula (I)
    Figure imgb0013
     wherein
    • Y =
    Figure imgb0014
     wherein R'1, R'2 and R'3 are each independently a hydrogen atom or a methyl group or an ethyl group, at least one of R'1, R'2 and R'3 being a methyl or an ethyl group,
    wherein the dotted lines represent a double bond and is present or not, and
    • R1, R2, R3, R4 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group, and
    • X is present or absent,
    • when X is present,
    o R5, R6, R7, R8, R9 are all present, and X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group
    • when X is absent, a double bond involving the carbon atom at the 4 position is present and
    o R7, R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
    o R5, R6, and R7 are present, and one of R8 or R9 is present and the other one is absent, or
    o R7 is a =C(R11)(R12) group and R5, R6, R8, R9 are present,
    • and when they are present, each of R5-R12 group is, independently, a hydrogen atom or a linear or branched C15 alkyl or C2-5 alkenyl group.
  2. Pyran derivatives of general formula (I) according to Claim 1 wherein
    • Y is one of (Y1), (Y2), (Y3) or (Y4) group
    Figure imgb0015
    Figure imgb0016
    • R1, R2, R3, R4 are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group, and
    • X is present or absent,
    • when X is present,
    o R5, R6, R7, R8, R9 are all present, and X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group
    • when X is absent, a double bond involving the carbon atom at the 4 position is present and
    o R7, R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
    o R5, R6, and R7 are present, and one of R8 or R9 is present and the other one is absent, or
    o R7 is a =C(R11)(R12) group and R5, R6, R8, R9 are present,
    • and when they are present, each of R5-R12 group is, independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  3. Pyran derivatives of general formula (I) according to Claims 1 or 2, wherein
    • Y is as defined in claims 1 or 2,
    • one of R3 or R4 is a hydrogen atom, and the other one is a methyl group
    • R7 is a =CH2 group and X is absent; or
    • R7 is a methyl group and X is present or absent ; when R7 is a methyl group and X is present, X is a hydrogen atom or an OZ group, wherein Z is a hydrogen atom or a R10 group or a C(O)R10 group; when R7 is a methyl group and X is absent, a double bond involving the carbon atom at the 4 position is present and
    o R8 and R9 are present, and one of R5 or R6 is present and the other one is absent, or
    o R5, R6, are present, and one of R8 or R9 is present and the other one is absent,
    • R1, R2 and R10 are, each independently, a hydrogen atom, or a linear or branched C1-5 alkyl or C2-5 alkenyl group
    • when present, R5, R6, R8, R9 are each a hydrogen atom.
  4. Pyran derivatives of general formula (I) according to Claim 1, wherein said derivatives are selected in the group comprising 4-methylene-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopent-3-enylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran, 4-methylene-2-(2,2,3-trimethylcyclopentylmethyl)-tetrahydropyran, 4-methyl-6-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-2-(2,2,3-trimethyl-cyclopentylmethyl)-3,6-dihydro-2H-pyran, 4-methyl-4-(3-methyl-but-3-enyloxy)-2-(2,2,3-trimethyl-cyclopentylmethyl)-tetrahydropyran.
  5. A process for the preparation of pyran derivatives of formula (I) as described in anyone of claims 1 to 4, said process being characterized in that a compound of general formula (A)
    Figure imgb0017
     wherein
    • Y is as defined in claim 1,
    • R1 and R2 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl or C2-5alkenyl group,
    is reacted, in presence of an acid, with a compound of general formula (B)
    Figure imgb0018
     wherein
    R3, R4, R5, R6, R7, R8 and R9 are, each independently, a hydrogen atom or a linear or branched C1-5 alkyl group, or a linear or branched C2-5 alkenyl group.
  6. The process as claimed in claim 5, further comprising a step to convert the aldehyde (A) into an acetal of general formula (C)
    Figure imgb0019
     wherein
    • Y is as defined in claim 1,
    • R1, R2, are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    • Z is a R10 group wherein R10 is a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    prior to the reaction with the alcohol (B).
  7. The process as claimed in claims 5 and 8, wherein compound (A) or compound (C) is reacted with compound (B), in presence of an acid, to produce the compounds of formula (I) wherein X is OZ, Z being a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  8. The process as claimed in claim 5, wherein compound (A) is reacted with compound (B), in presence of an acid, and the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I) wherein X is absent, and then subjected to an esterification reaction, in order to obtain compounds of formula (I) wherein X is OC(O)R10.
  9. The process as claimed in Claim 5, wherein compound (A) is reacted with compound (B), in presence of an acid, and the compounds of formula (I), wherein X is OH, are separated from the compounds of formula (I) wherein X is absent and then subjected to an alkylation reaction in order to obtain compounds of formula (I) wherein X is OZ, Z being a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  10. Composition comprising at least one compound of formula (II), and/or at least one compound of general formula (III) and/or at least one compound of general formula (IV), and optionally (V) and/or (VI)
    Figure imgb0020
    Figure imgb0021
     wherein
    • Y is
    Figure imgb0022
     wherein R'1, R'2 and R'3 are each independently a hydrogen atom or a methyl group or an ethyl group, at least one of R'1, R'2 and R'3 being a methyl or an ethyl group,
    wherein the dotted lines represent a double bond and is present or not,
    • R1, R2, R3, R4, R5, R6, R7, R8, R9 are, each independently, a hydrogen atom, a linear or branched C1-5 alkyl or C2-5 alkenyl group,
    • Z is a hydrogen atom or a linear or branched C1-5 alkyl or C2-5 alkenyl group or a group C(O)R10 wherein R10 is a linear or branched C1-5 alkyl or C2-5 alkenyl group.
  11. Use of a pyran derivative according to anyone of claims 1 to 4, or of a composition according to Claim 10 in perfumery for the preparation of perfumed bases and concentrates, fragrances, perfumes; topic compositions; cosmetic compositions selected in the group comprising face and body creams, cleansers, facial treatments, talc powders, hair oils, shampoos, hair lotions, bath oils and salts, shower and bath gels, soaps, body anti-perspirants and deodorizers, pre-shave, shaving and post-shave creams and lotions, creams, toothpastes, mouth baths, pomades; cleaning products, selected in the group comprising softeners, detergents, air deodorizers and household cleaning supplies.
  12. Use of a pyran derivative according to anyone of claims 1 to 4, or of a composition according to Claim 10, as flavouring agents for the preparation of flavouring compositions or articles, selected in the group comprising drinks, dairy products, ice creams, soups, sauces, dips, dishes, meat products, culinary assistances, salted biscuits or snacks and also beers, wines and tobaccos.
  13. Use of a pyran derivative according to anyone of claims 1 to 4, or of a composition according to Claim 10, as masking agents of odours and/or flavours, in a pharmaceutical, cosmetic or food composition.
  14. Use of a pyran derivative according to anyone of claims 1 to 4, or of a composition according to Claim 10, in combination with other perfumed or flavoured ingredients, solvents, additives or fixatives.
EP07847567.0A 2006-12-01 2007-11-30 Pyran derivatives, process of preparation and use thereof in perfumery and flavouring Active EP2125767B1 (en)

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PL07847567T PL2125767T3 (en) 2006-12-01 2007-11-30 Pyran derivatives, process of preparation and use thereof in perfumery and flavouring
EP07847567.0A EP2125767B1 (en) 2006-12-01 2007-11-30 Pyran derivatives, process of preparation and use thereof in perfumery and flavouring

Applications Claiming Priority (4)

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US86196606P 2006-12-01 2006-12-01
EP06291857A EP1927593A1 (en) 2006-12-01 2006-12-01 Pyran derivates, process of preparation and use thereof in perfumery and flavouring
PCT/EP2007/063051 WO2008065181A2 (en) 2006-12-01 2007-11-30 Pyran derivatives, process of preparation and use thereof in perfumery and flavouring
EP07847567.0A EP2125767B1 (en) 2006-12-01 2007-11-30 Pyran derivatives, process of preparation and use thereof in perfumery and flavouring

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EP2906545B1 (en) * 2012-10-15 2016-09-21 Basf Se Method for integrated production of 2-substituted 4-hydroxy-4-methyl tetrahydropyrans and of 2-substituted 4-methyl tetrahydropyrans
EP2865676A1 (en) * 2014-04-14 2015-04-29 Basf Se Preparation of 2-substituted 4-methyl-tetrahydropyranes from starting materials containing 2-alkyl-4,4-dimethyl-1,3-dioxane
WO2016074118A1 (en) 2014-11-10 2016-05-19 Givaudan Sa Improvements in or relating to organic compounds
US9850191B2 (en) * 2015-03-27 2017-12-26 International Flavors & Fragrances Inc. Aldehyde compounds and their use in perfume compositions
EP3572487A1 (en) 2018-05-25 2019-11-27 Basf Se 2-furyl- and 2-thienyl-substituted di- and tetrahydropyrans for use as aroma chemicals

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FR1013862A (en) * 1950-03-06 1952-08-05 Rhone Poulenc Sa New gamma-ethylenic ethers-oxides and their manufacturing process
NL6802619A (en) 1968-02-23 1969-08-26
JPS5817175B2 (en) * 1975-07-07 1983-04-05 オオツカセイヤク カブシキガイシヤ Ether Kagobutsuno Seizouhou
CH655932A5 (en) 1983-02-24 1986-05-30 Firmenich & Cie Pyran derivatives, process for their preparation and their use for the preparation of aliphatic alcohols
JPS61178977A (en) * 1985-01-23 1986-08-11 Kao Corp Pyran derivative, production thereof and perfume composition containing same
US4963285A (en) 1989-02-09 1990-10-16 International Flavors & Fragrances Inc. 2,4,4-irisubstituted tetrahydro pyranyl esters and organoleptic uses thereof
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GB0216940D0 (en) 2002-07-20 2002-08-28 Givaudan Sa Improvements in or relating to organic compounds

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JP2010511016A (en) 2010-04-08
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WO2008065181A3 (en) 2008-07-24
JP5489721B2 (en) 2014-05-14
EP2125767A2 (en) 2009-12-02
MX2009005782A (en) 2009-10-14

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